Conductance studies on the interaction of D-glucose with alkali halides in water and formamide

The interaction of D-glucose with alkali halide in aqueous and formmide solutions has been studied by employing conductance measurements. Our results showed a break at the saturation temperature indicating a transition in the conductance values. This behaviour is explained in terms of solute-solvent interactions involved in the electrolyte-solvent-nonelectrolyte systems.     

Electrical conductivity study of the self-association of ionic surfactants in solution in ethyleneglycol,formic acid and formamide

The self-association of several cationic surfactants has been investigated by means of solubility and electrical conductivity measurements in ethyleneglycol, formic acid and formamide. Operational critical micelle concentrations (CMC_op) have been obtained from the vs. surfactant concentrationC plots by the usual interpolation procedure. It has been found that for the surfactant-solvent systems investigated the value of CMC_op increases with the extent of theC-range investigated. This result together with others concerning the effect of temperature and surfactant chain length reveal that the CMC_op-values have an ambiguous meaning concerning the surfactant self-association. Comparison of the vs.C plots for cetyltrimethylammonium chloride and tetramethylammonium chloride, for instance, reveals that some surfactant self-association takes place, probably leading to small, highly ionized surfactant aggregates, but the systems do not show true critical micelle concentration. Solubility measurements as a function of temperature lead to the same conclusion. The results are discussed according to our present understanding of the process of micellization and the necessity of using solvents of very high cohesive energy density in order to observe, with ionic surfactants, true CMCs corresponding to a highly cooperative association process. This appears to be the case only with water and hydrazine, not with formamide and other less cohesive solvents.     

Activity coefficients of ions in sodium halide solutions: Critical remarks

The fundamentals of an experimental method proposed by Zhuo et al. [1], to determine activity coefficients of sodium and halide ions in sodium halide solutions, are critically examined. It is shown that this method relies on a key hypothesis, which proves to be incorrect, about the liquid junction potential, whose value is assumed not to change when the concentration of the sample solution is changed. The direct consequence of this assumption is that results that are interpreted as the activity coefficients of sodium and halide ions are, instead, conventional values, which only depend on the mean activity coefficients and transport numbers, and have no connection with the activity coefficients of the respective ions.     

Ionic association in acetonitrile and in formamide

In a recent derivation of relaxation effects in the Debye-Hückel-Onsager theory of electrolyte conductance, with a length parameter a, terms are included which have been omitted in earlier treatments (see Appendix). The new expression was applied earlier in a reanalysis of conductance data for aqueous solutions and is applied here to solutions in acetonitrile and in formamide, representing respectively dielectric constants considerably lower and higher than water. As in aqueous solutions, a minimum standard deviation is found over a wide range of (K _A,a) pairs without much effect on A ₀ , so that only approximate determinations ofK _A are possible. On the whole, the most appropriate length parametera is the physical contact distance between counterions, not a fixed radius, independent of ionic size, such as the Bjerrum value, nor a much larger radiusR serving as a boudary between free and associated ions in the ionic atmosphere about a central ion. Relaxation effects calculated by the new analysis are smaller than those from previous expressions for equal values ofa, and this leads to considerably larger values ofK _A than in the original papers. As a consequence, specific short-range ion-ion and ion-solvent forces in most solutions predominate over electrostatic attraction between counterions in their contribution toK _A. A table of limiting equivalent conductance based on the A ₀ values obtained is presented; this differs little from previous tables since A ₀ values obtained by the new analysis are similar to those obtained originally.     

Electrical conductance of aqueous solutions of KCl solutions at pressures up to 2000 atm

Electrical conductance measurements are reported for aqueous KCl solutions at 25°C as a function of concentration up to 0.02 M and pressure up to 2000 atm. The data from 103 runs were analyzed with the Fuoss-Hsia-Fernandez-Prini (FHFP) equation. The standard error of fit varies from 0.018 at 1 atm to 0.12 at 2000 atm. The increase of with pressure arises from increasing nonrandomness in the distribution of errors about the FHFP equation, suggesting that modifications in the theory are necessary. Departures from the Walden product for KCl as a function of pressure are compared with MgSO₄ and CaSO₄ in aqueous solutions.     

Reaction of alkyl halide salts of nitrogen-containing heterocycles with sulfur dioxide in aqueous solutions

Complexes of quaternary salts with SO₂ are formed on saturation of aqueous solutions of alkyl halide salts of nitrogen-containing heterocycles with sulfur dioxide. The SO₂ concentration necessary for the precipitation of the complexes increases in the order I < Br < Cl and decreases as the alkyl group attached to the nitrogen becomes larger. The sulfur dioxide in the complexes is bonded through the halide ion by a charge-transfer coordinate bond, and their separation into an independent phase is due to a change in the degree of hydration during complexing. Several crystalline adducts are described, and the autooxidation of the SO₂ complex of pyridine methiodide is investigated.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 966–969, July, 1972.     

An alternative interpretation of the chemical shift of the water proton in aqueous tetraalkylammonium halide solutions at various temperatures

An alternative explanation of the behavior of proton magnetic resonance chemical shifts of the water proton in aqueous tetraalkylammonium salt solutions is presented. It involves independent ion-solvent interactions and rapid exchange on the NMR time scale with the bulk water. Our explanation fits the known data and clearly shows why the observed chemical shift is linear with molality at low concentrations.     

Ionic radii in aqueous solutions

The aqueous ionic radii of 35 ions have been calculated from published data of the average distances between the ions and the nearest water molecules, obtained by diffraction and computer simulation methods.     

Additivity of the hydrogen bridges in several polymers of formamide

The purpose of the study was to examine the energy additivity of the hydrogen bridges in formamide polymers. Consideration was given to both the linear polymers observed in polypeptides, and to the cyclic polymers observed in the crystal structure. Additivity was found in several geometries. The linear polymers were considered as far as the tetramer, and the cyclic as far as the heptamer.Work supported in part by the Instituto Fisica, Universidad Nacional Autónoma de Mexico and Conacyt, México.     

Water structure in aqueous solutions of alkali halide salts: FTIR spectroscopy of the OD stretching band

Water structure making/breaking studies in solutions of five alkali halide salts (KF, KI, NaI, CsF and CsCl) in 4 wt% D(2)O in H(2)O mixtures have been performed by FTIR analysis of the OD stretching band in the full solubility range. The proposed method gives a microscopic picture of the water structure making/breaking character of the salts in terms of the hydrogen bonding between the water molecules in the solution. With the exception of CsCl, there is a very good correlation of the structure making/breaking character of the salts determined by FTIR analysis, and the viscosity coefficients of the solutions. The results fully support and explain previous studies of bubble attachment to microscopic salt particles of the above salts. The investigations support the primary importance of interfacial water structure in the explanation of the flotation of alkali halide salts in their brines.     

Acid-base chemistry of omeprazole in aqueous solutions

Omeprazole is a potent anti-acid drug. Its absorption and mode of action are closely related to its prototropic behavior. In the present study, omeprazole samples from different sources and in different forms were studied spectrophotometrically to obtain pK_a values. In the neutral to alkaline pH region, two consistent pK_a values of 7.1 and 14.7 were obtained from various samples. The assignment of these pK_a values was realized by comparison with the prototropic properties of N(1)-methylated omeprazole substituted on the nitrogen at the 1-position of the benzimidazole ring, which was found to have a pK_a of 7.5. The omeprazole pK_a of 14.7 is assigned to the dissociation of the hydrogen from the 1-position of the benzimidazole ring and the pK_a of 7.1 is assigned to the dissociation from the protonated pyridine nitrogen of omeprazole. The results presented are at variance with those of earlier work.     

Electrical conductivity in solid solutions and in two-phase regions of the silver halide-bivalent metal (cadmium,cobalt, zinc) halide systems

Electrical conductivity of solid systems AgX-MX₂ (where M=Cd, Co, Zn and X=Cl, Br) were measured in a large range of temperature and compositions. Activation energies and conductivity values vs. composition are presented and discussed in relation to phase equilibria in the respective systems. Maximum of the conductivity value and stabilization of the activation energy have been found for silver halides doped heavily with divalent cation e.g. in the systems forming solid solutions on the silver halide side. Disorder in AgBr on the approach to melting, expected to be higher than in AgCl, has been shown by means of original DSC curves presented for both halides.     

Computer-controlled measurement of thermal conductivities of aqueous salt solutions

A computer-controlled method to measure liquid thermal conductivities is described, and data are presented for aqueous electrolyte solutions. The relative thermal conductivities of sodium chloride and sodium iodide solutions agree well with previously published results. The effect of temperature on the thermal conductivity was investigated, and it was found that in the range 23–67°C the relative thermal conductivity was invariant with temperature within the experimental error (less than 1%). For a given concentration of 1-1 electrolyte, the relative thermal conductivity was found to vary linearly with the molecular weight of the solute.     

Effect of simple electrolytes on the thermodynamic properties of room temperature ionic liquids in aqueous solutions

Density, sound velocity and conductivity measurements are carried out on 1-heptyl-3-methylimidazolium bromide ([C₇mim][Br]) in pure water and in aqueous solutions of sodium di-hydrogen citrate, di-sodium hydrogen citrate and tri-sodium citrate over a range of temperatures at atmospheric pressure. The experimental density and sound velocity data are used to calculate the apparent molar volume and isentropic compressibility as a function of temperature and concentration. The effects of temperature and charge on the anion of sodium citrate salts on the apparent molar volume and isentropic compressibility of [C₇mim][Br] are studied. It was found that both of the apparent molar volume and isentropic compressibility of [C₇mim][Br] in aqueous sodium citrate solutions are larger than those in pure water and increase by increasing temperature. The effects of temperature and charge on the anion of sodium citrate salts on the conductivity behavior of the investigated IL solutions are also studied.     

The ionic product of water in highly concentrated aqueous electrolyte solutions

Summary The ionic product of water, , has been determined in aqueous NaCl (0.5–5.0M), KCl (3.0M), NaNO₃ (3.0 and 5.0M), and KNO₃ (2.5M) at 25 °C from high-precision potentiometric titrations carried out in cells with liquid junction using either glass or hydrogen electrodes. Measurements ofK _w provide a set of self-consistent data that can be used in the estimation of activity coefficient changes and liquid junction potentials in the study of extremely concentrated electrolyte solutions. Where comparison is possible, results obtained by hydrogen electrode measurements are in excellent agreement (ca ± 0.005 inpK _w) with other reliable experimental values and the predictions of thePitzer activity-coefficient model. The glass electrode results are, as expected, routinely lower (by 0.03–0.05pK _w units), owing to interference by Na⁺ ions. This effect virtually disappears in solutions of potassium salts. Comparison of the experimental results with thePitzer predictions shows that knowledge of the ternary interaction parameters is essential to account for specific ionic effects in the concentration dependence ofpK _w.On leave from the Abteilung für Physikalische Chemie und Theoretische Hüttenkunde, Montanuniversität Leoben, A-8700 Leoben, Austria     

Solvatochromic relationship: Prediction of distribution of ionic solutes in aqueous two-phase systems

Partition ratios of several ionic compounds in 20 different polymer/polymer aqueous two-phase systems (ATPS) containing 0.15 M NaCl in 0.01 M phosphate buffer, pH 7.4, were determined. The differences between the electrostatic properties of the phases in all the ATPS were estimated from partitioning of the homologous series of dinitrophenylated-amino acids. Also the solvatochromic solvent parameters characterizing the solvent dipolarity/polarizability (π*), solvent hydrogen-bond donor acidity (α), and solvent hydrogen-bond acceptor basicity (β) of aqueous media were measured in the coexisting phases of the ATPS. The solute-specific coefficients for the compounds examined were determined by the multiple linear regression analysis using the modified linear solvation energy relationship equation. The minimal number of ATPS necessary for determination of the coefficients was established and 10 ATPS were selected as a reference ATPS set. The solute-specific coefficients values obtained with this reference set of ATPS were used to predict the partition ratios for the compounds in 10 ATPS not included in the reference set. The predicted partition ratios values were compared to those determined experimentally and found to be in good agreement. It is concluded that the presented model of solute–solvent interactions as the driving force for solute partitioning in polymer/polymer ATPS describes experimental observations with 90–95% accuracy.     

离子液体双水相萃取分离苋菜红的研究

建立了由亲水性离子液体四氟硼酸1-丁基-3-甲基咪唑([Bmim]BF4)和NaH2PO4形成的双水相体系萃取分离苋菜红的新方法.研究了盐的浓度、离子液体浓度、溶液酸度、其它共存物质对苋菜红萃取率的影响.结果表明,NaH2PO4加入量在2～2.5 g,离子液量在1.0～2.0 mL,苋菜红溶液量在1.5 mL,溶液酸度在pH 4～6范围,离子液体双水相体系对苋菜红有较高的萃取率(E%＞90).用加入无机离子、不同类型表面活性剂和吸收光谱探讨了离子液体与苋菜红之间的作用.     

Sonoluminescence of aqueous solutions of lanthanide salts

The influence of salts (TbCl₃, Tb(NO₃)₃, PrCl₃, EuCl₃, CeCl₃, and DyCl₃) on the spectrum and intensity of multi-bubble sonoluminescence (SL) of water was observed at a frequency of 20 kHz. Luminescence bands of the lanthanide ions were detected in the SL spectra of concentrated solutions of the Ce^III, Tb^III, and Dy^III chlorides (0.1—1 mol L^–1). No luminescence was observed for solutions of the other salts, and the shape of the spectra is due to the absorption of the water SL by the lanthanide ions. Possible mechanisms of the appearance of SL of lanthanides were considered. The first mechanism is the excitation of the lanthanide aqua ions in the solution bulk due to the absorption of the short-wave portion of glow of the excited water molecules and OH radicals emitted from the cavitation gas-vapor bubbles. The second mechanism involves the transfer of the lanthanide ions to the gas phase from the liquid layer adjacent to the cavitation bubble and their excitation in the bubble volume upon collisions with other hot or electron-excited particles.